Lubricating oil compositions with improved deposit resistance and methods thereof

ABSTRACT

Provided is a lubricating oil composition and method of using such a composition that provides for improved high temperature deposit resistance. The composition includes a lubricating oil base stock at from 20 to 95 wt % of the composition, at least one ashless organic friction modifier at from 0.1 to 20 wt % of the composition, and at least one overbased detergent at from 0.1 to 20 wt % of the composition. The remainder of composition includes one or more other lubricating oil additives. The deposit resistance of the lubricating oil composition as measured by TEOST 33C total deposits is at least 20% lower than the deposit resistance for a comparable lubricating oil composition not including the combination of the at least one ashless organic friction modifier and the at least one overbased detergent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/772,360, filed on Nov. 28, 2018, the entire contents of which areincorporated herein by reference.

FIELD

This disclosure relates to lubricating oils with improved depositresistance and in particular, high temperature deposit resistance, andmethods of making and using such lubricating oils. The lubricating oilsinclude one or more ashless organic friction modifiers in combinationwith one or more overbased detergents. The lubricating oils are usefulas passenger vehicle engine oil (PVEO) products or commercial vehicleengine oil (CVEO) products.

BACKGROUND

Lubricating oils for internal combustion engines contain in addition toat least one base lubricating oil, additives which enhance theperformance of the lubricating oil. A variety of additives such asantioxidants, detergents, dispersants, friction modifiers, viscositymodifiers, corrosion inhibitors, antiwear additives, pour pointdepressants, seal swell additives, and antifoam agents are used inlubricating oil compositions.

During engine operation, oil insoluble oxidation byproducts areproduced. Deposit formation in a lubricating oil will lead to thedeposits eventually falling out of the oil and depositing on thesurfaces for lubrication, which negatively impacts the performance ofthe oil. Dispersants help keep these byproducts in solution, thusdiminishing their deposit on metal surfaces. Dispersants may be ashlessor ash-forming (non-ashless) in nature. So called ashless dispersantsare organic materials that form substantially no ash upon combustion.

A known class of dispersants is the alkenylsuccinic derivatives,typically produced by the reaction of a long chain substituted alkenylsuccinic compound, usually a substituted succinic anhydride, with apolyhydroxy or polyamino compound. The long chain group constituting theoleophilic portion of the molecule which confers solubility in the oil,is normally a polyisobutylene group. Many examples of this type ofdispersant are well known commercially and in the literature.

Engine cleanliness is a critical performance attribute of modern enginelubricants. A well-known engine cleanliness test is the TEOST 33C (ASTMD6335) deposit bench test, which is designed to simulate temperaturesexperienced in turbochargers.

Auto builders are faced with challenging emission requirements and CAFErequirements, and therefore are broadly deploying turbocharged engines.Turbochargers are exposed to engine exhaust gas and operate at speeds of100,000 rpm or higher. As a result of these operating conditions,generation of deposits on the turbocharged engine surfaces greatlydeteriorates engine performance. Therefore, there is a need forlubricating oils that when used with turbocharged passenger vehicleengines and turbocharged commercial vehicle engines provide for animprovement in high temperature deposit formation, deposit resistanceand cleanliness performance. There is also a need for lubricating oilsthat provide for improvement cleanliness of mechanical componentslubricated by such oils.

SUMMARY

This disclosure relates to lubricating oils which provide surprising andunexpected improvements in deposit resistance (in particular hightemperature deposit resistance) and cleanliness and methods of makingand using such lubricating oils. The lubricating oils of this disclosureinclude one or more ashless organic friction modifiers in combinationwith one or more overbased detergents that provide improvements incleanliness performance. The disclosure also relates to methods of usingsuch lubricating oils to improve passenger vehicle engine and commercialvehicle engine performance and in particular for turbocharged engines.

In one form the instant disclosure, a lubricating oil compositioncomprises: a lubricating oil base stock at from 20 to 95 wt % of thecomposition, at least one ashless organic friction modifier at from 0.1to 20 wt % of the composition, at least one overbased detergent at from0.1 to 20 wt % of the composition, and wherein the remainder of thelubricating oil composition includes one or more other lubricating oiladditives. The at least one ashless organic friction modifier isselected from the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane; a polymeric organic friction modifiercontaining PIBSA, glycerol and oligomerized ethylene oxide andcombinations thereof. The deposit resistance of the lubricating oilcomposition as measured by TEOST 33C total deposits (ASTM D6335) is atleast 20% lower than the deposit resistance for a comparable lubricatingoil composition not including the combination of the at least oneashless organic friction modifier and the at least one overbaseddetergent.

In another form the instant disclosure, a method for improving the hightemperature deposit resistance of a lubricating oil composition for usein lubricating a mechanical component comprises: providing a lubricatingoil composition to a mechanical component, wherein the lubricating oilcomposition comprises: a lubricating oil base stock at from 20 to 95 wt% of the composition, at least one ashless organic friction modifier atfrom 0.1 to 20 wt % of the composition, at least one overbased detergentat from 0.1 to 20 wt % of the composition, and wherein the remainder ofthe lubricating oil composition includes one or more other lubricatingoil additives. The at least one ashless organic friction modifier isselected from the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane; a polymeric organic friction modifiercontaining PIBSA, glycerol and oligomerized ethylene oxide andcombinations thereof. The method provides a deposit resistance asmeasured by TEOST 33C total deposits (ASTM D6335) that is at least 20%lower than the deposit resistance for a comparable lubricating oilcomposition not including the combination of the at least one ashlessorganic friction modifier and the at least one overbased detergent.

Other objects and advantages of the present disclosure will becomeapparent from the detailed description and drawings that follow.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a tabular depiction of TEOST 33C results for partiallyformulated lubricating oil compositions of the Examples includingvarious base stocks and combinations of high TBN calcium salicylatedetergent and ashless organic friction modifier.

FIG. 2 shows a tabular depiction of TEOST 33C results for partiallyformulated lubricating oil compositions of the Examples including acombination of various high TBN detergents and ashless organic frictionmodifier with a 4 cSt PAO base stock.

FIG. 3 shows a tabular depiction of TEOST 33C results for partiallyformulated lubricating oil compositions of the Examples includingvarious friction modifiers in combination with a high TBN calciumsalicylate detergent in a 4 cSt PAO base stock.

FIG. 4 shows a tabular depiction of TEOST 33C results for partiallyformulated lubricating oil compositions of the Examples including acombination of high TBN calcium salicylate detergent in combination withan ashless organic friction modifier at various loadings (0 to 1 wt. %of the partially formulated oil) in a 4 cSt PAO base stock.

FIG. 5 shows a graphical depiction of TEOST 33C results versus ashlessorganic friction modifier loading for the partially formulatedlubricating oil compositions of the Examples of FIG. 4.

DETAILED DESCRIPTION Definitions

“About” or “approximately.” All numerical values within the detaileddescription and the claims herein are modified by “about” or“approximately” the indicated value, and take into account experimentalerror and variations that would be expected by a person having ordinaryskill in the art.

“Alkyl” as it relates to the ashless organic friction modifiers includesstraight-chain or branched alkyl groups, such as, methyl, ethyl,n-propyl, i-propyl or the different butyl, pentyl or hexyl isomers.

“Alkenyl” as it relates to the ashless organic friction modifiersincludes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.

“Alkylcarbonyl” as it relates to the ashless organic friction modifiersdenotes a straight-chain or branched alkyl moieties bonded to a C(═O)moiety. Examples of “alkylcarbonyl” include CH₃C(═O)—, CH₃CH₂CH₂C)═O)—and (CH₃)₂CHC(═O)—.

“Major amount” as it relates to components included within thelubricating oils of the specification and the claims means greater thanor equal to 50 wt. %, or greater than or equal to 60 wt. %, or greaterthan or equal to 70 wt. %, or greater than or equal to 80 wt. %, orgreater than or equal to 90 wt. % based on the total weight of thelubricating oil.

“Minor amount” as it relates to components included within thelubricating oils of the specification and the claims means less than 50wt. %, or less than or equal to 40 wt. %, or less than or equal to 30wt. %, or greater than or equal to 20 wt. %, or less than or equal to 10wt. %, or less than or equal to 5 wt. %, or less than or equal to 2 wt.%, or less than or equal to 1 wt. %, based on the total weight of thelubricating oil.

“Essentially free” as it relates to components included within thelubricating oils of the specification and the claims means that theparticular component is at 0 weight % within the lubricating oil, oralternatively is at impurity type levels within the lubricating oil(less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or lessthan 1 ppm).

“Other lubricating oil additives” as used in the specification and theclaims means other lubricating oil additives that are not specificallyrecited in the particular section of the specification or the claims.For example, other lubricating oil additives may include, but are notlimited to, antioxidants, detergents, dispersants, antiwear additives,corrosion inhibitors, viscosity modifiers, metal passivators, pour pointdepressants, seal compatibility agents, antifoam agents, extremepressure agents, friction modifiers and combinations thereof.

“Hydrocarbon” refers to a compound consisting of carbon atoms andhydrogen atoms.

“Alkane” refers to a hydrocarbon that is completely saturated. An alkanecan be linear, branched, cyclic, or substituted cyclic.

“Olefin” refers to a non-aromatic hydrocarbon comprising one or morecarbon-carbon double bond in the molecular structure thereof.

“Mono-olefin” refers to an olefin comprising a single carbon-carbondouble bond.

“Cn” group or compound refers to a group or a compound comprising carbonatoms at total number thereof of n. Thus, “Cm-Cn” group or compoundrefers to a group or compound comprising carbon atoms at a total numberthereof in the range from m to n. Thus, a C1-C50 alkyl group refers toan alkyl group comprising carbon atoms at a total number thereof in therange from 1 to 50.

“Carbon backbone” refers to the longest straight carbon chain in themolecule of the compound or the group in question. “Branch” refer to anysubstituted or unsubstituted hydrocarbyl group connected to the carbonbackbone. A carbon atom on the carbon backbone connected to a branch iscalled a “branched carbon.”

“Epsilon-carbon” in a branched alkane refers to a carbon atom in itscarbon backbone that is (i) connected to two hydrogen atoms and twocarbon atoms and (ii) connected to a branched carbon via at least four(4) methylene (CH₂) groups. Quantity of epsilon carbon atoms in terms ofmole percentage thereof in a alkane material based on the total moles ofcarbon atoms can be determined by using, e.g., ¹³C NMR.

“SAE” refers to SAE International, formerly known as Society ofAutomotive Engineers, which is a professional organization that setsstandards for internal combustion engine lubricating oils.

“SAE J300” refers to the viscosity grade classification system of enginelubricating oils established by SAE, which defines the limits of theclassifications in rheological terms only.

“Base stock” or “base oil” interchangeably refers to an oil that can beused as a component of lubricating oils, heat transfer oils, hydraulicoils, grease products, and the like.

“Lubricating oil” or “lubricant” interchangeably refers to a substancethat can be introduced between two or more surfaces to reduce the levelof friction between two adjacent surfaces moving relative to each other.A lubricant base stock is a material, typically a fluid at variouslevels of viscosity at the operating temperature of the lubricant, usedto formulate a lubricant by admixing with other components. Non-limitingexamples of base stocks suitable in lubricants include API Group I,Group II, Group III, Group IV, and Group V base stocks. PAOs,particularly hydrogenated PAOs, have recently found wide use inlubricants as a Group IV base stock, and are particularly preferred. Ifone base stock is designated as a primary base stock in the lubricant,additional base stocks may be called a co-base stock.

All kinematic viscosity values in this disclosure are as determinedpursuant to ASTM D445. Kinematic viscosity at 100° C. is reported hereinas KV100, and kinematic viscosity at 40° C. is reported herein as KV40.Unit of all KV100 and KV40 values herein is cSt unless otherwisespecified.

All viscosity index (“VI”) values in this disclosure are as determinedpursuant to ASTM D2270.

All Noack volatility (“NV”) values in this disclosure are as determinedpursuant to ASTM D5800 unless specified otherwise. Unit of all NV valuesis wt %, unless otherwise specified.

All pour point values in this disclosure are as determined pursuant toASTM D5950 or D97.

All CCS viscosity (“CCSV”) values in this disclosure are as determinedpursuant to ASTM 5293. Unit of all CCSV values herein is millipascalsecond (mPa·s), which is equivalent to centipoise), unless specifiedotherwise. All CCSV values are measured at a temperature of interest tothe lubricating oil formulation or oil composition in question. Thus,for the purpose of designing and fabricating engine oil formulations,the temperature of interest is the temperature at which the SAE J300imposes a minimal CCSV.

All percentages in describing chemical compositions herein are by weightunless specified otherwise. “Wt. %” means percent by weight.

Lubricating Oil Compositions and Methods of this Disclosure

It has been surprisingly found that, in accordance with this disclosuredeposit resistance (in particular high temperature deposit resistance)and engine cleanliness are improved for lubricating oils including oneor more ashless organic friction modifiers in combination with one ormore overbased detergents in comparison to comparable lubricating oilsnot including the combinations of one or more ashless organic frictionmodifiers and one or more overbased detergents disclosed herein.

In particular, it has been surprisingly found that, for lubricating oilsof this disclosure containing a lubricating oil base stock at from 20 to95 wt % of the composition, at least one ashless organic frictionmodifier at from 0.1 to 20 wt % of the composition, at least oneoverbased detergent at from 0.1 to 20 wt % of the composition, andwherein the remainder of the lubricating oil composition includes one ormore other lubricating oil additives provide for a deposit resistance asmeasured by TEOST 33C total deposits (ASTM D6335) that is at least 20%lower than the deposit resistance for a comparable lubricating oilcomposition not including the combination of the at least one ashlessorganic friction modifier and the at least one overbased detergent.

The at least one ashless organic friction modifier may be selected fromthe group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane; a polymeric organic friction modifiercontaining PIBSA, glycerol and oligomerized ethylene oxide andcombinations thereof.

For the at least one ashless organic friction modifier, it is preferableif it is selected from the group consisting of mixed mono-(47%),di-(33%) and tri-(20%) fatty acids using saturated C16 and C18 alkylchains, glycerol mono-, di- and tri-mixed oleate, propylene glycolstearyl ether, poly-hydroxylcarboxylic acid esters of polyalkylene oxidemodified polyols, n-tallow 1,3 diaminopropane, oleic acid, oleyl amide,and polymeric organic friction modifier containing PIBSA, glycerol andoligomerized ethylene oxide and combinations thereof.

In alternative forms, the deposit resistance as measured by TEOST 33Ctotal deposits (ASTM D6335) of the lubricating oil compositionsdisclosed herein is at least 100% lower, or at least 90% lower, or atleast 80% lower, or at least 70% lower, or at least 60% lower, or atleast 50% lower, or at least 40% lower, or at least 30% lower, or atleast 10% lower than a comparable lubricating oil composition notincluding the combination of one or more ashless organic frictionmodifiers and one or more overbased detergents disclosed herein.

The lubricating oil compositions disclosed herein provide a TEOST 33Cdeposits of less than or equal to 80 mg, or less than or equal to 70 mg,or less than or equal to 60 mg, or less than or equal to 50 mg, or lessthan or equal to 40 mg, or less than or equal to 30 mg, or less than orequal to 20 mg, or less than or equal to 10 mg. The benefit in TEOST 33Cdeposits (lower TEOST 33C values) provided by the lubricating oilcompositions including one or more ashless organic friction modifiers incombination with one or more overbased detergents in comparison tocomparable lubricating oil compositions not including the combinationsof one or more ashless organic friction modifiers and one or moreoverbased detergents disclosed is surprising and unexpected.

In accordance with this disclosure, a method is also provided to improvethe high temperature deposit resistance of a lubricating oil compositionfor use in lubricating a mechanical component comprising: providing alubricating oil composition to a mechanical component, wherein thelubricating oil composition comprises: a lubricating oil base stock atfrom 20 to 95 wt % of the composition, at least one ashless organicfriction modifier at from 0.1 to 20 wt % of the composition, at leastone overbased detergent at from 0.1 to 20 wt % of the composition, andwherein the remainder of the lubricating oil composition includes one ormore other lubricating oil additives. The method provides for a depositresistance as measured by TEOST 33C total deposits (ASTM D6335) that isat least 20% lower than the deposit resistance for a comparablelubricating oil composition not including the combination of the atleast one ashless organic friction modifier and the at least oneoverbased detergent. The at least one ashless organic friction modifiermay be selected from the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane; a polymeric organic friction modifiercontaining PIBSA, glycerol and oligomerized ethylene oxide andcombinations thereof.

For the at least one ashless organic friction modifier, it is preferablethat it is selected from the group consisting of mixed mono-(47%),di-(33%) and tri-(20%) fatty acids using saturated C16 and C18 alkylchains, glycerol mono-, di- and tri-mixed oleate, propylene glycolstearyl ether, poly-hydroxylcarboxylic acid esters of polyalkylene oxidemodified polyols, n-tallow 1,3 diaminopropane, oleic acid, oleyl amide,and polymeric organic friction modifier containing PIBSA, glycerol andoligomerized ethylene oxide and combinations thereof.

The method to improve high temperature deposit resistance of alubricating oil composition for use in lubricating a mechanicalcomponent provides a TEOST 33C deposits of less than or equal to 80 mg,or less than or equal to 70 mg, or less than or equal to 60 mg, or lessthan or equal to 50 mg, or less than or equal to 40 mg, or less than orequal to 30 mg, or less than or equal to 20 mg, or less than or equal to10 mg. The benefit in TEOST 33C deposits (lower TEOST 33C values)provided by the methods to improve high temperature deposit resistanceof a lubricating oil composition including one or more ashless organicfriction modifiers in combination with one or more overbased detergentsin comparison to comparable lubricating oil compositions not includingthe combinations of one or more ashless organic friction modifiers andone or more overbased detergents disclosed is surprising and unexpected.

The methods to improve deposit resistance of this disclosure provideadvantaged cleanliness performance in the lubrication of internalcombustion engines, power trains, drivelines, transmissions, gears, geartrains, gear sets, compressors, pumps, hydraulic systems, bearings,bushings, turbines, and the like. Also, the methods to improve depositresistance of this disclosure provide advantaged cleanliness performancein the lubrication of mechanical components, which can include, forexample, pistons, piston rings, cylinder liners, cylinders, cams,tappets, lifters, bearings (journal, roller, tapered, needle, ball, andthe like), gears, valves, and the like. Further, the lubricating oilcompositions of this disclosure provide advantaged cleanlinessperformance and deposit resistance as a component in lubricantcompositions, which can include, for example, lubricating liquids,semi-solids, solids, greases, dispersions, suspensions, materialconcentrates, additive concentrates, and the like.

Friction Modifiers

A friction modifier is any material or materials that can alter thecoefficient of friction of a surface lubricated by any lubricant orfluid containing such material(s). Friction modifiers, also known asfriction reducers, friction improvers, or lubricity agents or oilinessagents, and other such agents that change the ability of base oils,formulated lubricant compositions, or functional fluids, to modify thecoefficient of friction of a lubricated surface may be effectively usedin combination with the base oils or lubricant compositions of thepresent disclosure if desired. Friction modifiers that lower thecoefficient of friction are particularly advantageous in combinationwith the base oils and lube compositions of this disclosure.

Ashless organic friction modifiers are in included in the lubricatingoil compositions of this disclosure. In particular, the inventivelubricating oils of this disclosure include at least one ashless organicfriction modifier, which is incorporated at from 0.01 to 20 wt %, or0.05 to 18 wt %, or 0.1 to 15 wt %, or 0.3 to 10 wt %, or 0.5 to 5 wt %,or 0.6 to 4 wt %, or 0.7 to 3 wt %, or 0.8 to 2.5 wt %, or 0.9 to 2.0 wt%, or 1.0 to 1.5 wt % of the lubricating oil composition.

Ashless organic friction modifiers useful in this disclosure may includelubricant materials that contain effective amounts of polar groups, forexample, hydroxyl-containing hydrocarbyl base oils, glycerides, partialglycerides, glyceride derivatives, and the like. Polar groups infriction modifiers may include hydrocarbyl groups containing effectiveamounts of 0, N, S, or P, individually or in combination. Other frictionmodifiers that may be particularly effective include, for example, salts(both ash-containing and ashless derivatives) of fatty acids, fattyalcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates,and comparable synthetic long-chain hydrocarbyl acids, alcohols, amides,esters, hydroxy carboxylates, and the like. In some instances fattyorganic acids, fatty amines, and sulfurized fatty acids may be used assuitable friction modifiers.

Other illustrative friction modifiers useful in the lubricating engineoil formulations of this disclosure include, for example, alkoxylatedfatty acid esters, alkanolamides, polyol fatty acid esters, boratedglycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

Illustrative alkoxylated fatty acid esters include, for example,polyoxyethylene stearate, fatty acid polyglycol ester, and the like.These can include polyoxypropylene stearate, polyoxybutylene stearate,polyoxyethylene isosterate, polyoxypropylene isostearate,polyoxyethylene palmitate, and the like.

Illustrative alkanolamides include, for example, lauric aciddiethylalkanolamide, palmic acid diethylalkanolamide, and the like.These can include oleic acid diethyalkanolamide, stearic aciddiethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylatedhydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

Illustrative polyol fatty acid esters include, for example, glycerolmono-oleate, glycerol mono-, di- and tri-mixed oleate, saturated mono-,di-, and tri-glyceride esters, glycerol mono-stearate, and the like.These can include polyol esters, hydroxyl-containing polyol esters, andthe like.

Illustrative borated glycerol fatty acid esters include, for example,borated glycerol mono-oleate, borated glycerol mono-, di- and tri-mixedoleate, borated saturated mono-, di-, and tri-glyceride esters, boratedglycerol mono-sterate, and the like. In addition to glycerol polyols,these can include trimethylolpropane, pentaerythritol, sorbitan, and thelike. These esters can be polyol monocarboxylate esters, polyoldicarboxylate esters, and on occasion polyoltricarboxylate esters.Preferred can be the glycerol mono-oleates, glycerol dioleates, glyceroltrioleates, glycerol mono-, di- and tri-mixed oleates, glycerolmonostearates, glycerol distearates, and glycerol tristearates and thecorresponding glycerol monopalmitates, glycerol dipalmitates, andglycerol tripalmitates, and the respective isostearates, linoleates, andthe like. On occasion the glycerol esters can be preferred as well asmixtures containing any of these. Ethoxylated, propoxylated, butoxylatedfatty acid esters of polyols, especially using glycerol as underlyingpolyol can be preferred.

Illustrative fatty alcohol ethers include, for example, stearyl ether,myristyl ether, and the like. Alcohols, including those that have carbonnumbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylatedto form the corresponding fatty alkyl ethers. The underlying alcoholportion can preferably be stearyl, myristyl, C₁₁-C₁₃ hydrocarbon, oleyl,isosteryl, and the like.

In certain embodiments, the friction modifier comprises at least one ofa long chain alkly thiocarbamide, mixed glyceride ester (substituted orunsubstituted), ethoxylated fatty ester, phenyl, or combination thereof.In certain embodiments, the friction modifier is selected from the groupconsisting of a molybdenum-containing friction modifier (long chainalkyl thio carbamide molybdenum complex), a mono, di and/or trimester;mostly saturated C14, C16 & C18; an ethoxylated fatty ester; anester/ether block copolymer, and combinations thereof.

Advantageous ashless organic friction modifiers for the lubricating oilcompositions of the instant disclosure include the following:

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl.

In a preferable form of structure (1), A is CH₃ and B is a C16-C20 alkylgroup.

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl.

In a preferable form of structure (2), A is a C14-C20 alkylcarbonyl or aC14-C20 alkenylcarbonyl

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino.

In a preferable form of structure (3), A is a C14-C20 alkyl or a C14-C20alkenyl and B is oxygen.

Preferred ashless friction modifiers for the lubricating oilcompositions of the instant disclosure include mixed mono-(47%),di-(33%) and tri-(20%) fatty acids using saturated C16 and C18 alkylchains), a glycerol mono-, di- and tri-mixed oleate, a propylene glycolstearyl ether, a poly-hydroxylcarboxylic acid esters of polyalkyleneoxide modified polyols, n-tallow 1,3 diaminopropane, oleic acid, oleylamide, and a polymeric organic friction modifier containing PIBSA,glycerol and oligomerized ethylene oxide.

Other optional non-ashless (ash forming) inorganic friction modifiersfor use in combination with the at least one ashless organic frictionmodifier may include metal-containing compounds in combination with theashless organic friction modifiers disclosed herein. Illustrativemetal-containing friction modifiers may include, for example, inorganiccompounds or materials, or mixtures thereof. Illustrative optionalinorganic friction modifiers useful in the lubricating engine oilformulations of this disclosure include, for example, molybdenum amine,molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate,molybdenum dithiophosphates, molybdenum amine complexes, molybdenumcarboxylates, and the like, and mixtures thereof. Similar tungsten basedcompounds may be preferable.

Optional non-ashless (ash forming) metal-containing inorganic frictionmodifiers may include metal salts or metal-ligand complexes where themetals may include alkali, alkaline earth, or transition group metals.Such metal-containing friction modifiers may also have low-ashcharacteristics. Transition metals may include Mo, Sb, Sn, Fe, Cu, Zn,and others. Ligands may include hydrocarbyl derivative of alcohols,polyols, glycerols, partial ester glycerols, thiols, carboxylates,carbamates, thiocarbamates, dithiocarbamates, phosphates,thiophosphates, dithiophosphates, amides, imides, amines, thiazoles,thiadiazoles, dithiazoles, diazoles, triazoles, and other polarmolecular functional groups containing effective amounts of O, N, S, orP, individually or in combination. In particular, Mo-containingcompounds can be particularly effective such as for exampleMo-dithiocarbamates, Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines,Mo (Am), Mo-alcoholates, Mo-alcohol-amides, etc. See U.S. Pat. Nos.5,824,627; 6,232,276; 6,153,564; 6,143,701; 6,110,878; 5,837,657;6,010,987; 5,906,968; 6,734,150; 6,730,638; 6,689,725; 6,569,820; WO99/66013; WO 99/47629; WO 98/26030.

Useful concentrations of optional non-ashless (ash forming) frictionmodifiers may range from 0.01 weight percent to 5 weight percent, orabout 0.1 weight percent to about 2.5 weight percent, or about 0.1weight percent to about 1.5 weight percent, or about 0.1 weight percentto about 1 weight percent. Concentrations of molybdenum-containingmaterials are often described in terms of Mo metal concentration.Advantageous concentrations of Mo may range from 25 ppm to 700 ppm ormore, and often with a preferred range of 50-200 ppm. Friction modifiersof all types may be used in mixtures with the ashless organic frictionmodifiers of this disclosure. Often to mixtures of two or more frictionmodifiers, or mixtures of friction modifier(s) with alternate surfaceactive material(s), are also desirable.

Detergents

Illustrative detergents useful in the lubricating oil compositions ofthis disclosure include, for example, alkali metal detergents, alkalineearth metal detergents, or mixtures of one or more alkali metaldetergents and one or more alkaline earth metal detergents. A typicaldetergent is an anionic material that contains a long chain hydrophobicportion of the molecule and a smaller anionic or oleophobic hydrophilicportion of the molecule. The anionic portion of the detergent istypically derived from an organic acid such as a sulfur-containing acid,carboxylic acid (e.g., salicylic acid), phosphorus-containing acid,phenol, or mixtures thereof. The counterion is typically an alkalineearth or alkali metal. The detergent can be overbased as describedherein.

The detergent is preferably a metal salt of an organic or inorganicacid, a metal salt of a phenol, or mixtures thereof. The metal ispreferably selected from an alkali metal, an alkaline earth metal, andmixtures thereof. The organic or inorganic acid is selected from analiphatic organic or inorganic acid, a cycloaliphatic organic orinorganic acid, an aromatic organic or inorganic acid, and mixturesthereof.

The metal is preferably selected from an alkali metal, an alkaline earthmetal, and mixtures thereof. More preferably, the metal is selected fromcalcium (Ca), magnesium (Mg), and mixtures thereof.

The organic acid or inorganic acid is preferably selected from asulfur-containing acid, a carboxylic acid, a phosphorus-containing acid,and mixtures thereof.

Preferably, the metal salt of an organic or inorganic acid or the metalsalt of a phenol comprises calcium phenate, calcium sulfonate, calciumsalicylate, magnesium phenate, magnesium sulfonate, magnesiumsalicylate, an overbased detergent, and mixtures thereof.

Salts that contain a substantially stochiometric amount of the metal aredescribed as neutral salts and have a total base number (TBN, asmeasured by ASTM D2896) of from 0 to 80. Many compositions areoverbased, containing large amounts of a metal base that is achieved byreacting an excess of a metal compound (a metal hydroxide or oxide, forexample) with an acidic gas (such as carbon dioxide). Useful detergentscan be neutral, mildly overbased, or highly overbased. These detergentscan be used in mixtures of neutral, overbased, highly overbased calciumsalicylate, sulfonates, phenates and/or magnesium salicylate,sulfonates, phenates. The TBN ranges can vary from low, medium to highTBN products, including as low as 0 to as high as 600. Preferably theTBN delivered by the detergent is between 60 and 600, more preferablybetween 200 and 500, and even more preferably between 250 and 450.Mixtures of low, medium, high TBN can be used, along with mixtures ofcalcium and magnesium metal based detergents, and including sulfonates,phenates, salicylates, and carboxylates. A detergent mixture with ametal ratio of 1, in conjunction of a detergent with a metal ratio of 2,and as high as a detergent with a metal ratio of 5, can be used. Borateddetergents can also be used.

Alkaline earth phenates are another useful class of detergent. Thesedetergents can be made by reacting alkaline earth metal hydroxide oroxide (CaO, Ca(OH)₂, BaO, Ba(OH)₂, MgO, Mg(OH)₂, for example) with analkyl phenol or sulfurized alkylphenol. Useful alkyl groups includestraight chain or branched C₁-C₃₀ alkyl groups, preferably, C₄-C₂₀ ormixtures thereof. Examples of suitable phenols include isobutylphenol,2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It shouldbe noted that starting alkylphenols may contain more than one alkylsubstituent that are each independently straight chain or branched andcan be used from 0.5 to 6 weight percent. When a non-sulfurizedalkylphenol is used, the sulfurized product may be obtained by methodswell known in the art. These methods include heating a mixture ofalkylphenol and sulfurizing agent (including elemental sulfur, sulfurhalides such as sulfur dichloride, and the like) and then reacting thesulfurized phenol with an alkaline earth metal base.

In accordance with this disclosure, metal salts of carboxylic acids arepreferred detergents. These carboxylic acid detergents may be preparedby reacting a basic metal compound with at least one carboxylic acid andremoving free water from the reaction product. These compounds may beoverbased to produce the desired TBN level. Detergents made fromsalicylic acid are one preferred class of detergents derived fromcarboxylic acids. Useful salicylates include long chain alkylsalicylates. One useful family of compositions is of the formula

where R is an alkyl group having 1 to about 30 carbon atoms, n is aninteger from 1 to 4, and M is an alkaline earth metal. Preferred Rgroups are alkyl chains of at least C₁₁, preferably C₁₃ or greater. Rmay be optionally substituted with substituents that do not interferewith the detergent's function. M is preferably, calcium, magnesium,barium, or mixtures thereof. More preferably, M is calcium.

Hydrocarbyl-substituted salicylic acids may be prepared from phenols bythe Kolbe reaction (see U.S. Pat. No. 3,595,791). The metal salts of thehydrocarbyl-substituted salicylic acids may be prepared by doubledecomposition of a metal salt in a polar solvent such as water oralcohol.

Alkaline earth metal phosphates are also used as detergents and areknown in the art.

Detergents may be simple detergents or what is known as hybrid orcomplex detergents. The latter detergents can provide the properties oftwo detergents without the need to blend separate materials. See U.S.Pat. No. 6,034,039.

Preferred detergents include calcium sulfonates, magnesium sulfonates,calcium salicylates, magnesium salicylates, calcium phenates, magnesiumphenates, and other related components (including borated detergents),and mixtures thereof. Preferred mixtures of detergents include magnesiumsulfonate and calcium salicylate, magnesium sulfonate and calciumsulfonate, magnesium sulfonate and calcium phenate, calcium phenate andcalcium salicylate, calcium phenate and calcium sulfonate, calciumphenate and magnesium salicylate, calcium phenate and magnesium phenate.Overbased detergents are also preferred in terms of having a high TBN inthe range of between 200 and 600. A particularly preferred detergent forthe lubricating oil compositions of the instant disclosure is a 350 TBNcalcium salicylate. A 400 TBN magnesium sulfonate, a 400 TBN calciumsulfonate, a 255 TBN calcium phenate and a 68 TBN calcium salicylatedetergent have also provided advantageous performance in the lubricatingoil compositions of the instant disclosure.

The detergent concentration in the lubricating oil compositions of thisdisclosure can range from 0.1 to 20 wt %, or 0.2 to 15 wt %, or 0.3 to10 wt %, or 0.4 to 8.0 wt %, or 0.5 to 6.0 wt %, or 0.8 to 4 wt %, or1.0 to 3.0 wt %, or 1.2 to 2.5 wt %, or 1.5 to 2.0 wt %, based on thetotal weight of the lubricating oil composition.

As used herein, the detergent concentrations are given on an “asdelivered” basis. Typically, the active detergent is delivered with aprocess oil. The “as delivered” detergent typically contains from about20 weight percent to about 100 weight percent, or from about 40 weightpercent to about 60 weight percent, of active detergent in the “asdelivered” detergent product.

Lubricating Oil Base Stocks

A wide range of lubricating oil base stocks can be used in conjunctionwith the at least one organic ashless friction modifier and the at leastone over based detergent of the lubricating oils disclosed herein. Suchbase stocks can be either derived from natural resources or synthetic,including un-refined, refined, or re-refined oils. Un-refined oil basestocks include shale oil obtained directly from retorting operations,petroleum oil obtained directly from primary distillation, and ester oilobtained directly from a natural source (such as plant matters andanimal tissues) or directly from a chemical esterification process.Refined oil base stocks are those un-refined base stocks furthersubjected to one or more purification steps such as solvent extraction,secondary distillation, acid extraction, base extraction, filtration,and percolation to improve the at least one lubricating oil property.Re-refined oil base stocks are obtained by processes analogous torefined oils but using an oil that has been previously used as a feedstock.

Groups I, II, III, IV and V are broad base oil stock categoriesdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for lubricant baseoils. Group I base stocks have a viscosity index of between about 80 to120 and contain greater than about 0.03% sulfur and/or less than about90% saturates. Group II base stocks have a viscosity index of betweenabout 80 to 120, and contain less than or equal to about 0.03% sulfurand greater than or equal to about 90% saturates. Group III stocks havea viscosity index greater than about 120 and contain less than or equalto about 0.03% sulfur and greater than about 90% saturates. Group IVincludes polyalphaolefins (PAO). Group V base stock includes base stocksnot included in Groups I-IV. The table below summarizes properties ofeach of these five groups.

Base Oil Properties Saturates Sulfur Viscosity Index Group I <90 and/or >0.03% and ≥80 and <120 Group II ≥90 and ≤0.03% and ≥80 and <120 GroupIII ≥90 and ≤0.03% and ≥120 Group IV polyalphaolefins (PAO) Group V Allother base oil stocks not included in Groups I, II, III or IV

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful. Natural oils vary also as to the method used fortheir production and purification, for example, their distillation rangeand whether they are straight run or cracked, hydrorefined, or solventextracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks,including synthetic oils such as alkyl aromatics and synthetic estersare also well known base stock oils.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oilssuch as polymerized and interpolymerized olefins (polybutylenes,polypropylenes, propylene isobutylene copolymers, ethylene-olefincopolymers, and ethylene-alphaolefin copolymers, for example).Polyalphaolefin (PAO) oil base stocks are commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₈, C₁₀, C₁₂, C₁₄olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.4,956,122; 4,827,064; and 4,827,073.

The number average molecular weights of the PAOs, which are knownmaterials and generally available on a major commercial scale fromsuppliers such as ExxonMobil Chemical Company, Chevron Phillips ChemicalCompany, BP, and others, typically vary from about 250 to about 3,000,although PAO's may be made in viscosities up to about 150 cSt (100° C.).The PAOs are typically comprised of relatively low molecular weighthydrogenated polymers or oligomers of alphaolefins which include, butare not limited to, C₂ to about C₃₂ alphaolefins with the C₈ to aboutC₁₆ alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like,being preferred. The preferred polyalphaolefins are poly-1-octene,poly-1-decene and poly-1-dodecene and mixtures thereof and mixedolefin-derived polyolefins. However, the dimers of higher olefins in therange of C₁₄ to C₁₈ may be used to provide low viscosity base stocks ofacceptably low volatility. Depending on the viscosity grade and thestarting oligomer, the PAOs may be predominantly trimers and tetramersof the starting olefins, with minor amounts of the higher oligomers,having a viscosity range of 1.5 to 12 cSt. PAO fluids of particular usemay include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof.Mixtures of PAO fluids having a viscosity range of 1.5 to approximately150 cSt or more may be used if desired.

The PAO fluids may be conveniently made by the polymerization of analphaolefin in the presence of a polymerization catalyst such as theFriedel-Crafts catalysts including, for example, aluminum trichloride,boron trifluoride or complexes of boron trifluoride with water, alcoholssuch as ethanol, propanol or butanol, carboxylic acids or esters such asethyl acetate or ethyl propionate. For example the methods disclosed byU.S. Pat. Nos. 4,149,178 or 3,382,291 may be conveniently used herein.Other descriptions of PAO synthesis are found in the following U.S. Pat.Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156;4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C14 toC18 olefins are described in U.S. Pat. No. 4,218,330.

Other useful lubricant oil base stocks include wax isomerate base stocksand base oils, comprising hydroisomerized waxy stocks (e.g. waxy stockssuch as gas oils, slack waxes, fuels hydrocracker bottoms, etc.),hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocksand base oils, and other wax isomerate hydroisomerized base stocks andbase oils, or mixtures thereof. Fischer-Tropsch waxes, the high boilingpoint residues of Fischer-Tropsch synthesis, are highly paraffinichydrocarbons with very low sulfur content. The hydroprocessing used forthe production of such base stocks may use an amorphoushydrocracking/hydroisomerization catalyst, such as one of thespecialized lube hydrocracking (LHDC) catalysts or a crystallinehydrocracking/hydroisomerization catalyst, preferably a zeoliticcatalyst. For example, one useful catalyst is ZSM-48 as described inU.S. Pat. No. 5,075,269, the disclosure of which is incorporated hereinby reference in its entirety. Processes for makinghydrocracked/hydroisomerized distillates andhydrocracked/hydroisomerized waxes are described, for example, in U.S.Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as inBritish Patent Nos. 1,429,494; 1,350,257; 1,440,230 and 1,390,359. Eachof the aforementioned patents is incorporated herein in their entirety.Particularly favorable processes are described in European PatentApplication Nos. 464546 and 464547, also incorporated herein byreference. Processes using Fischer-Tropsch wax feeds are described inU.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures of which areincorporated herein by reference in their entirety.

Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized (wax isomerate) base oils beadvantageously used in the instant disclosure, and may have usefulkinematic viscosities at 100° C. of about 3 cSt to about 50 cSt,preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt toabout 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about4.0 cSt at 100° C. and a viscosity index of about 141. TheseGas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized base oils may have useful pourpoints of about −20° C. or lower, and under some conditions may haveadvantageous pour points of about −25° C. or lower, with useful pourpoints of about −30° C. to about −40° C. or lower. Useful compositionsof Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived baseoils, and wax-derived hydroisomerized base oils are recited in U.S. Pat.Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and areincorporated herein in their entirety by reference.

The hydrocarbyl aromatics can be used as a base oil or base oilcomponent and can be any hydrocarbyl molecule that contains at leastabout 5% of its weight derived from an aromatic moiety such as abenzenoid moiety or naphthenoid moiety, or their derivatives. Thesehydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyldiphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylatedbis-phenol A, alkylated thiodiphenol, and the like. The aromatic can bemono-alkylated, dialkylated, polyalkylated, and the like. The aromaticcan be mono- or poly-functionalized. The hydrocarbyl groups can also becomprised of mixtures of alkyl groups, alkenyl groups, alkynyl,cycloalkyl groups, cycloalkenyl groups and other related hydrocarbylgroups. The hydrocarbyl groups can range from about C₆ up to about C₆₀with a range of about C₈ to about C₂₀ often being preferred. A mixtureof hydrocarbyl groups is often preferred, and up to about three suchsubstituents may be present. The hydrocarbyl group can optionallycontain sulfur, oxygen, and/or nitrogen containing substituents. Thearomatic group can also be derived from natural (petroleum) sources,provided at least about 5% of the molecule is comprised of an above-typearomatic moiety. Viscosities at 100° C. of approximately 3 cSt to about50 cSt are preferred, with viscosities of approximately 3.4 cSt to about20 cSt often being more preferred for the hydrocarbyl aromaticcomponent. In one embodiment, an alkyl naphthalene where the alkyl groupis primarily comprised of 1-hexadecene is used. Other alkylates ofaromatics can be advantageously used. Naphthalene or methyl naphthalene,for example, can be alkylated with olefins such as octene, decene,dodecene, tetradecene or higher, mixtures of similar olefins, and thelike. Useful concentrations of hydrocarbyl aromatic in a lubricant oilcomposition can be about 2% to about 25%, preferably about 4% to about20%, and more preferably about 4% to about 15%, depending on theapplication.

Alkylated aromatics such as the hydrocarbyl aromatics of the presentdisclosure may be produced by well-known Friedel-Crafts alkylation ofaromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G.A. (ed.), Inter-science Publishers, New York, 1963. For example, anaromatic compound, such as benzene or naphthalene, is alkylated by anolefin, alkyl halide or alcohol in the presence of a Friedel-Craftscatalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1,chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-sciencePublishers, New York, 1964. Many homogeneous or heterogeneous, solidcatalysts are known to one skilled in the art. The choice of catalystdepends on the reactivity of the starting materials and product qualityrequirements. For example, strong acids such as AlCl₃, BF₃, or HF may beused. In some cases, milder catalysts such as FeCl₃ or SnCl₄ arepreferred. Newer alkylation technology uses zeolites or solid superacids.

Esters comprise a useful base stock. Additive solvency and sealcompatibility characteristics may be secured by the use of esters suchas the esters of dibasic acids with monoalkanols and the polyol estersof monocarboxylic acids. Esters of the former type include, for example,the esters of dicarboxylic acids such as phthalic acid, succinic acid,alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.,with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, etc. Specific examples of these types ofesters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexylfumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.

Particularly useful synthetic esters are those which are obtained byreacting one or more polyhydric alcohols, preferably the hinderedpolyols (such as the neopentyl polyols, e.g., neopentyl glycol,trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylolpropane, pentaerythritol and dipentaerythritol) with alkanoic acidscontaining at least about 4 carbon atoms, preferably C5 to C30 acidssuch as saturated straight chain fatty acids including caprylic acid,capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,arachic acid, and behenic acid, or the corresponding branched chainfatty acids or unsaturated fatty acids such as oleic acid, or mixturesof any of these materials.

Suitable synthetic ester components include the esters of trimethylolpropane, trimethylol butane, trimethylol ethane, pentaerythritol and/ordipentaerythritol with one or more monocarboxylic acids containing fromabout 5 to about 10 carbon atoms. These esters are widely availablecommercially, for example, the Mobil P-41 and P-51 esters of ExxonMobilChemical Company.

Also useful are esters derived from renewable material such as coconut,palm, rapeseed, soy, sunflower and the like. These esters may bemonoesters, di-esters, polyol esters, complex esters, or mixturesthereof. These esters are widely available commercially, for example,the Esterex NP 343 ester of ExxonMobil Chemical Company.

More particularly, branched polyol esters comprise a useful base stockof this disclosure. The branched polyol esters are obtained by reactingone or more polyhydric alcohols, preferably the hindered polyols (suchas the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane,2-methyl-2-propyl-1,3-propanediol, trimethylol propane, pentaerythritoland dipentaerythritol) with single or mixed branched mono-carboxylicacids containing at least about 4 carbon atoms, preferably C₅ to C₃₀branched mono-carboxylic acids including 2,2-dimethyl propionic acid(neopentanoic acid), neoheptanoic acid, neooctanoic acid, neononanoicacid, iso-hexanoic acid, neodecanoic acid, 2-ethyl hexanoic acid (2EH),3,5,5-trimethyl hexanoic acid (TMH), isoheptanoic acid, isooctanoicacid, isononanoic acid, isodecanoic acid, or mixtures of any of thesematerials. These branched polyol esters include fully converted andpartially converted polyol esters.

Particularly useful polyols include, for example, neopentyl glycol,2,2-dimethylol butane, trimethylol ethane, trimethylol propane,trimethylol butane, mono-pentaerythritol, technical gradepentaerythritol, di-pentaerythritol, tri-pentaerythritol, ethyleneglycol, propylene glycol and polyalkylene glycols (e.g., polyethyleneglycols, polypropylene glycols, 1,4-butanediol, sorbitol and the like,2-methylpropanediol, polybutylene glycols, etc., and blends thereof suchas a polymerized mixture of ethylene glycol and propylene glycol). Themost preferred alcohols are technical grade (e.g., approximately 88%mono-, 10% di- and 1-2% tri-pentaerythritol) pentaerythritol,mono-pentaerythritol, di-pentaerythritol, neopentyl glycol andtrimethylol propane.

Particularly useful branched mono-carboxylic acids include, for example,2,2-dimethyl propionic acid (neopentanoic acid), neoheptanoic acid,neooctanoic acid, neononanoic acid, iso-hexanoic acid, neodecanoic acid,2-ethyl hexanoic acid (2EH), 3,5,5-trimethyl hexanoic acid (TMH),isoheptanoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid,or mixtures of any of these materials. One especially preferred branchedacid is 3,5,5-trimethyl hexanoic acid. The term “neo” as used hereinrefers to a trialkyl acetic acid, i.e., an acid which is triplysubstituted at the alpha carbon with alkyl groups.

Preferably, the branched polyol ester is derived from a polyhydricalcohol and a branched mono-carboxylic acid. In particular, the branchedpolyol ester is obtained by reacting one or more polyhydric alcoholswith one or more branched mono-carboxylic acids containing at leastabout 4 carbon atoms.

Preferred branched polyol esters useful in this disclosure include, forexample, mono-pentaerythritol ester of branched mono-carboxylic acids,di-pentaerythritol ester of branched mono-carboxylic acids,trimethylolpropane ester of C8-C10 acids, and the like.

Other synthetic esters that can be useful in this disclosure are thosewhich are obtained by reacting one or more polyhydric alcohols,preferably the hindered polyols (such as the neopentyl polyols, e.g.,neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,trimethylol propane, pentaerythritol and dipentaerythritol) with monocarboxylic acids containing at least about 4 carbon atoms, preferablybranched C₅ to C₃₀ acids including caprylic acid, capric acid, lauricacid, myristic acid, palmitic acid, stearic acid, arachic acid, andbehenic acid, or the corresponding branched chain fatty acids orunsaturated fatty acids such as oleic acid, or mixtures of any of thesematerials.

Other ester base oils useful in this disclosure include adipate esters.The dialkyl adipate ester is derived from adipic acid and a branchedalkyl alcohol.

Mixtures of branched polyol ester base stocks with other lubricating oilbase stocks (e.g., Groups I, II, III, IV and V base stocks) may beuseful in the lubricating oil formulations of this disclosure.

The branched polyol ester can be present in an amount of from about 1 toabout 50 weight percent, or from about 5 to about 45 weight percent, orfrom about 10 to about 40 weight percent, or from about 15 to about 35weight percent, or from about 20 to about 30 weight percent, based onthe total weight of the formulated oil.

Engine oil formulations containing renewable esters are included in thisdisclosure. For such formulations, the renewable content of the ester istypically greater than about 70 weight percent, preferably more thanabout 80 weight percent and most preferably more than about 90 weightpercent.

Other useful fluids of lubricating viscosity include non-conventional orunconventional base stocks that have been processed, preferablycatalytically, or synthesized to provide high performance lubricationcharacteristics.

Non-conventional or unconventional base stocks/base oils include one ormore of a mixture of base stock(s) derived from one or moreGas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate basestock(s) derived from natural wax or waxy feeds, mineral and ornon-mineral oil waxy feed stocks such as slack waxes, natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, or other mineral, mineraloil, or even non-petroleum oil derived waxy materials such as waxymaterials received from coal liquefaction or shale oil, and mixtures ofsuch base stocks.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce lube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized cat and/or solvent dewaxedsynthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxyhydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (orsolvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from about 2 mm²/s to about 50 mm²/s(ASTM D445). They are further characterized typically as having pourpoints of −5° C. to about −40° C. or lower (ASTM D97). They are alsocharacterized typically as having viscosity indices of about 80 to about140 or greater (ASTM D2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than about 10 ppm, and more typically less than about 5ppm of each of these elements. The sulfur and nitrogen content of GTLbase stock(s) and/or base oil(s) obtained from F-T material, especiallyF-T wax, is essentially nil. In addition, the absence of phosphorus andaromatics make this materially especially suitable for the formulationof low SAP products.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

Base oils for use in the formulated lubricating oils useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, and Group V oils and mixturesthereof, preferably API Group II, Group III, Group IV, and Group V oilsand mixtures thereof, more preferably the Group III to Group V base oilsdue to their exceptional volatility, stability, viscometric andcleanliness features. Minor quantities of Group I stock, such as theamount used to dilute additives for blending into formulated lube oilproducts, can be tolerated but should be kept to a minimum, i.e. amountsonly associated with their use as diluent/carrier oil for additives usedon an “as-received” basis. Even in regard to the Group II stocks, it ispreferred that the Group II stock be in the higher quality rangeassociated with that stock, i.e. a Group II stock having a viscosityindex in the range 100<VI<120. Groups II and III base stocks can beincluded in the lubricating oil formulations of this disclosure, butpreferably only those with high quality, e.g., those having a VI from100 to 120. Group IV and V base stocks, preferably those of highquality, are desirably included into the lubricating oil formulations ofthis disclosure.

The base oil or base stock constitutes the major component or majoramount of the lubricating oil compositions of the present disclosure andtypically is present in an amount ranging from about 5 to about 99weight percent, or about 7 to about 95 weight percent, or about 10 toabout 90 weight percent, or about 20 to about 80 weight percent,preferably from about 70 to about 95 weight percent, and more preferablyfrom about 85 to about 95 weight percent, based on the total weight ofthe composition. The base oil or base stock may be selected from any ofthe synthetic or natural oils typically used as crankcase lubricatingoils for spark-ignited and compression-ignited engines.

The base oil or base stock conveniently has a kinematic viscosity,according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm²/s)at 100° C. and preferably of about 2.5 cSt to about 9 cSt (or mm²/s) at100° C.

Mixtures of synthetic and natural base oils may be used if desired.Bi-modal mixtures of Group I, II, III, IV, and/or V base stocks may beused if desired. A second base stock or co-base stock may be alsooptionally incorporated into the lubricating oil compositions of thisdisclosure in an amount ranging from about 5 to about 80 weight percent,or about 10 to about 60 weight percent, or about 15 to about 50 weightpercent, or about 20 to about 40 weight percent, or from about 25 toabout 35 weight percent.

Other Lubricating Oil Additives of the Lubricating Oil Compositions ofthis Disclosure

The lubricating oil compositions (preferably lubricating oilformulations) of this disclosure may additionally contain one or more ofthe commonly used other lubricating oil performance additives includingbut not limited to dispersants, viscosity modifiers, antiwear additives,corrosion inhibitors, rust inhibitors, metal deactivators, extremepressure additives, anti-seizure agents, wax modifiers, fluid-lossadditives, seal compatibility agents, lubricity agents, anti-stainingagents, chromophoric agents, defoamants, demulsifiers, densifiers,wetting agents, gelling agents, tackiness agents, colorants, and others.For a review of many commonly used additives and the quantities used,see: (i) Klamann in Lubricants and Related Products, Verlag Chemie,Deerfield Beach, Fla.; ISBN 0-89573-177-0; (ii) “Lubricant Additives,”M. W. Ranney, published by Noyes Data Corporation of Parkridge, N J(1973); (iii) “Synthetics, Mineral Oils, and Bio-Based Lubricants,”Edited by L. R. Rudnick, CRC Taylor and Francis, 2006, ISBN1-57444-723-8; (iv) “Lubrication Fundamentals”, J. G. Wills, MarcelDekker Inc., (New York, 1980); (v) Synthetic Lubricants andHigh-Performance Functional Fluids, 2nd Ed., Rudnick and Shubkin, MarcelDekker Inc., (New York, 1999); and (vi) “Polyalphaolefins,” L. R.Rudnick, Chemical Industries (Boca Raton, Fla., United States) (2006),111 (Synthetics, Mineral Oils, and Bio-Based Lubricants), 3-36.Reference is also made to: (a) U.S. Pat. No. 7,704,930 B2; (b) U.S. Pat.No. 9,458,403 B2, Column 18, line 46 to Column 39, line 68; (c) U.S.Pat. No. 9,422,497 B2, Column 34, line 4 to Column 40, line 55; and (d)U.S. Pat. No. 8,048,833 B2, Column 17, line 48 to Column 27, line 12,the disclosures of which are incorporated herein in its entirety. Theseadditives are commonly delivered with varying amounts of diluent oilthat may range from 5 wt % to 50 wt % based on the total weight of theadditive package before incorporation into the formulated oil.

Further details of the other lubricating oil additives useful in thelubricating oil compositions of this disclosure are as follows:

Viscosity Modifiers

Viscosity modifiers provide lubricants with high and low temperatureoperability. These additives impart shear stability at elevatedtemperatures and acceptable viscosity at low temperatures.

Non-limiting exemplary viscosity modifiers for the inventive lubricatingoils are as follows: high molecular weight hydrocarbons, polyesters andviscosity modifier dispersants that function as both a viscositymodifier and a dispersant. Typical molecular weights of these polymersare between about 10,000 to 1,500,000, more typically about 20,000 to1,200,000, and even more typically between about 50,000 and 1,000,000.

Other examples of suitable viscosity modifiers are linear or star-shapedpolymers and copolymers of methacrylate, butadiene, olefins, oralkylated styrenes. Polyisobutylene is a commonly used viscositymodifier. Another suitable viscosity modifier is polymethacrylate(copolymers of various chain length alkyl methacrylates, for example),some formulations of which also serve as pour point depressants. Othersuitable viscosity modifiers include copolymers of ethylene andpropylene, hydrogenated block copolymers of styrene and isoprene, andpolyacrylates (copolymers of various chain length acrylates, forexample). Specific examples include styrene-isoprene orstyrene-butadiene based polymers of 50,000 to 200,000 molecular weight.

Olefin copolymers are commercially available from Chevron OroniteCompany LLC under the trade designation “PARATONE®” (such as “PARATONE®8921” and “PARATONE® 8941”); from Afton Chemical Corporation under thetrade designation “HiTEC®” (such as “HiTEC® 5850B”; and from TheLubrizol Corporation under the trade designation “Lubrizol® 7067C”.Hydrogenated polyisoprene star polymers are commercially available fromInfineum International Limited, e.g., under the trade designation“SV200” and “SV600”. Hydrogenated diene-styrene block copolymers arecommercially available from Infineum International Limited, e.g., underthe trade designation “SV 50”.

The polymethacrylate or polyacrylate polymers can be linear polymerswhich are available from Evonik Industries under the trade designation“Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which areavailable from Lubrizol Corporation under the trade designation Asteric™(e.g., Lubrizol 87708 and Lubrizol 87725).

Illustrative vinyl aromatic-containing polymers as viscosity modifiersuseful in this disclosure may be derived predominantly from vinylaromatic hydrocarbon monomer. Illustrative vinyl aromatic-containingcopolymers useful in this disclosure may be represented by the followinggeneral formula:

A−B

wherein A is a polymeric block derived predominantly from vinyl aromatichydrocarbon monomer, and B is a polymeric block derived predominantlyfrom conjugated diene monomer.

In another embodiment of this disclosure, the at least one viscositymodifier may be used in an amount of less than about 20 weight percent,or less than about 15 weight percent, or less than about 10 weightpercent, or less than about 7 weight percent, or less than about 5weight percent, and in certain instances, may be used at less than 2weight percent, or less than about 1 weight percent, or less than about0.5 weight percent, based on the total weight of the formulated oil orlubricating engine oil. The preferred range for the at least oneviscosity modifier is from 5 to 20 wt % of the formulated oil.

Viscosity modifiers are typically added as concentrates, in largeamounts of diluent oil. As used herein, the viscosity modifierconcentrations are given on an “as delivered” basis. Typically, theactive polymer is delivered with a diluent oil. The “as delivered”viscosity modifier typically contains from 20 weight percent to 75weight percent of an active polymer for polymethacrylate or polyacrylatepolymers, or from 8 weight percent to 20 weight percent of an activepolymer for olefin copolymers, hydrogenated polyisoprene star polymers,or hydrogenated diene-styrene block copolymers, in the “as delivered”polymer concentrate.

Antiwear Additives

A metal alkylthiophosphate and more particularly a metal dialkyl dithiophosphate in which the metal constituent is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be a useful component of the lubricating oils ofthis disclosure. ZDDP can be derived from primary alcohols, secondaryalcohols or mixtures thereof. ZDDP compounds generally are of theformula

Zn[SP(S)(OR¹)(OR²)]₂

where R¹ and R² are C₁-C₁₈ alkyl groups, preferably C₂-C₁₂ alkyl groups.These alkyl groups may be straight chain or branched. Alcohols used inthe ZDDP can be 2-propanol, butanol, secondary butanol, pentanols,hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, and the like. Mixtures of secondary alcoholsor of primary and secondary alcohol can be preferred. Alkyl aryl groupsmay also be used.

Preferable zinc dithiophosphates which are commercially availableinclude secondary zinc dithiophosphates such as those available from forexample, The Lubrizol Corporation under the trade designations “LZ677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite underthe trade designation “OLOA 262” and from for example Afton Chemicalunder the trade designation “HITEC 7169”.

The ZDDP is typically used in amounts of from about 0.4 weight percentto about 1.2 weight percent, preferably from about 0.5 weight percent toabout 1.0 weight percent, and more preferably from about 0.6 weightpercent to about 0.8 weight percent, based on the total weight of thelubricating oil, although more or less can often be used advantageously.Preferably, the ZDDP is a secondary ZDDP and present in an amount offrom about 0.6 to 1.0 weight percent of the total weight of thelubricating oil.

Low phosphorus engine oil formulations are included in this disclosure.For such formulations, the phosphorus content is typically less thanabout 0.12 weight percent preferably less than about 0.10 weight percentand most preferably less than about 0.085 weight percent.

Dispersants

During engine operation, oil-insoluble oxidation byproducts areproduced. Dispersants help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Dispersants used in theformulation of the lubricating oil may be ashless or ash-forming innature. Preferably, the dispersant is ashless. So called ashlessdispersants are organic materials that form substantially no ash uponcombustion. For example, non-metal-containing or borated metal-freedispersants are considered ashless. In contrast, metal-containingdetergents discussed herein form ash upon combustion.

Suitable dispersants typically contain a polar group attached to arelatively high molecular weight hydrocarbon chain. The polar grouptypically contains at least one element of nitrogen, oxygen, orphosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

A particularly useful class of dispersants are the (poly)alkenylsuccinicderivatives, typically produced by the reaction of a long chainhydrocarbyl substituted succinic compound, usually a hydrocarbylsubstituted succinic anhydride, with a polyhydroxy or polyaminocompound. The long chain hydrocarbyl group constituting the oleophilicportion of the molecule which confers solubility in the oil, is normallya polyisobutylene group. Many examples of this type of dispersant arewell known commercially and in the literature. Exemplary U.S. patentsdescribing such dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707;3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012;3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersantare described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Afurther description of dispersants may be found, for example, inEuropean Patent Application No. 471 071, to which reference is made forthis purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substitutedsuccinic anhydride derivatives are useful dispersants. In particular,succinimide, succinate esters, or succinate ester amides prepared by thereaction of a hydrocarbon-substituted succinic acid compound preferablyhaving at least 50 carbon atoms in the hydrocarbon substituent, with atleast one equivalent of an alkylene amine are particularly useful.

Succinimides are formed by the condensation reaction between hydrocarbylsubstituted succinic anhydrides and amines. Molar ratios can varydepending on the polyamine. For example, the molar ratio of hydrocarbylsubstituted succinic anhydride to TEPA can vary from about 1:1 to about5:1. Representative examples are shown in U.S. Pat. Nos. 3,087,936;3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800;and Canada Patent No. 1,094,044.

Succinate esters are formed by the condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alcohols or polyols.Molar ratios can vary depending on the alcohol or polyol used. Forexample, the condensation product of a hydrocarbyl substituted succinicanhydride and pentaerythritol is a useful dispersant.

Succinate ester amides are formed by condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alkanol amines. Forexample, suitable alkanol amines include ethoxylatedpolyalkylpolyamines, propoxylated polyalkylpolyamines andpolyalkenylpolyamines such as polyethylene polyamines. One example ispropoxylated hexamethylenediamine. Representative examples are shown inU.S. Pat. No. 4,426,305.

The molecular weight of the hydrocarbyl substituted succinic anhydridesused in the preceding paragraphs will typically range between 800 and2,500 or more. The above products can be post-reacted with variousreagents such as sulfur, oxygen, formaldehyde, carboxylic acids such asoleic acid. The above products can also be post reacted with boroncompounds such as boric acid, borate esters or highly borateddispersants, to form borated dispersants generally having from about 0.1to about 5 moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which isincorporated herein by reference. Process aids and catalysts, such asoleic acid and sulfonic acids, can also be part of the reaction mixture.Molecular weights of the alkylphenols range from 800 to 2,500.Representative examples are shown in U.S. Pat. Nos. 3,697,574;3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.

Typical high molecular weight aliphatic acid modified Mannichcondensation products useful in this disclosure can be prepared fromhigh molecular weight alkyl-substituted hydroxyaromatics or HNR₂group-containing reactants.

Hydrocarbyl substituted amine ashless dispersant additives are wellknown to one skilled in the art; see, for example, U.S. Pat. Nos.3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.

Preferred dispersants include borated and non-borated succinimides,including those derivatives from mono-succinimides, bis-succinimides,and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbylsuccinimide is derived from a hydrocarbylene group such aspolyisobutylene having a Mn of from about 500 to about 5000, or fromabout 1000 to about 3000, or about 1000 to about 2000, or a mixture ofsuch hydrocarbylene groups, often with high terminal vinylic groups.Other preferred dispersants include succinic acid-esters and amides,alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives,and other related components.

Polymethacrylate or polyacrylate derivatives are another class ofdispersants. These dispersants are typically prepared by reacting anitrogen containing monomer and a methacrylic or acrylic acid esterscontaining 5-25 carbon atoms in the ester group. Representative examplesare shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylateand polyacrylate dispersants are normally used as multifunctionalviscosity modifiers. The lower molecular weight versions can be used aslubricant dispersants or fuel detergents.

Illustrative preferred dispersants useful in this disclosure includethose derived from polyalkenyl-substituted mono- or dicarboxylic acid,anhydride or ester, which dispersant has a polyalkenyl moiety with anumber average molecular weight of at least 900 and from greater than1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferablyfrom greater than 1.3 to 1.5, functional groups (mono- or dicarboxylicacid producing moieties) per polyalkenyl moiety (a medium functionalitydispersant). Functionality (F) can be determined according to thefollowing formula:

F=(SAP×M_(n))/((112,200×A.I.)−(SAP×98))

wherein SAP is the saponification number (i.e., the number of milligramsof KOH consumed in the complete neutralization of the acid groups in onegram of the succinic-containing reaction product, as determinedaccording to ASTM D94); M_(n) is the number average molecular weight ofthe starting olefin polymer; and A.I. is the percent active ingredientof the succinic-containing reaction product (the remainder beingunreacted olefin polymer, succinic anhydride and diluent).

The polyalkenyl moiety of the dispersant may have a number averagemolecular weight of at least 900, suitably at least 1500, preferablybetween 1800 and 3000, such as between 2000 and 2800, more preferablyfrom about 2100 to 2500, and most preferably from about 2200 to about2400. The molecular weight of a dispersant is generally expressed interms of the molecular weight of the polyalkenyl moiety. This is becausethe precise molecular weight range of the dispersant depends on numerousparameters including the type of polymer used to derive the dispersant,the number of functional groups, and the type of nucleophilic groupemployed.

Polymer molecular weight, specifically M_(n), can be determined byvarious known techniques. One convenient method is gel permeationchromatography (GPC), which additionally provides molecular weightdistribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly,“Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, NewYork, 1979). Another useful method for determining molecular weight,particularly for lower molecular weight polymers, is vapor pressureosmometry (e.g., ASTM D3592).

The polyalkenyl moiety in a dispersant preferably has a narrow molecularweight distribution (MWD), also referred to as polydispersity, asdetermined by the ratio of weight average molecular weight (M_(w)) tonumber average molecular weight (M_(n)). Polymers having a M_(w)/M_(n)of less than 2.2, preferably less than 2.0, are most desirable. Suitablepolymers have a polydispersity of from about 1.5 to 2.1, preferably fromabout 1.6 to about 1.8.

Suitable polyalkenes employed in the formation of the dispersantsinclude homopolymers, interpolymers or lower molecular weighthydrocarbons. One family of such polymers comprise polymers of ethyleneand/or at least one C₃ to C₂ alpha-olefin having the formula H₂C═CHR¹wherein R¹ is a straight or branched chain alkyl radical comprising 1 to26 carbon atoms and wherein the polymer contains carbon-to-carbonunsaturation, and a high degree of terminal ethenylidene unsaturation.Preferably, such polymers comprise interpolymers of ethylene and atleast one alpha-olefin of the above formula, wherein R¹ is alkyl of from1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbonatoms, and more preferably still of from 1 to 2 carbon atoms.

Another useful class of polymers is polymers prepared by cationicpolymerization of monomers such as isobutene and styrene. Commonpolymers from this class include polyisobutenes obtained bypolymerization of a C₄ refinery stream having a butene content of 35 to75% by wt., and an isobutene content of 30 to 60% by wt. A preferredsource of monomer for making poly-n-butenes is petroleum feedstreamssuch as Raffinate II. These feedstocks are disclosed in the art such asin U.S. Pat. No. 4,952,739. A preferred embodiment utilizespolyisobutylene prepared from a pure isobutylene stream or a Raffinate Istream to prepare reactive isobutylene polymers with terminal vinylideneolefins. Polyisobutene polymers that may be employed are generally basedon a polymer chain of from 1500 to 3000.

The dispersant(s) are preferably non-polymeric (e.g., mono- orbis-succinimides). Such dispersants can be prepared by conventionalprocesses such as disclosed in U.S. Patent Application Publication No.2008/0020950, the disclosure of which is incorporated herein byreference.

The dispersant(s) can be borated by conventional means, as generallydisclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and 5,430,105.

Such dispersants may be used in an amount of about 0.01 to 20 weightpercent or 0.01 to 10 weight percent, preferably about 0.5 to 8 weightpercent, or more preferably 0.5 to 4 weight percent. Or such dispersantsmay be used in an amount of about 2 to 12 weight percent, preferablyabout 4 to 10 weight percent, or more preferably 6 to 9 weight percent.On an active ingredient basis, such additives may be used in an amountof about 0.06 to 14 weight percent, preferably about 0.3 to 6 weightpercent. The hydrocarbon portion of the dispersant atoms can range fromC₆₀ to C₁₀₀₀, or from C₇₀ to C₃₀₀, or from C₇₀ to C₂₀₀. Thesedispersants may contain both neutral and basic nitrogen, and mixtures ofboth. Dispersants can be end-capped by borates and/or cyclic carbonates.Nitrogen content in the finished oil can vary from about 200 ppm byweight to about 2000 ppm by weight, preferably from about 200 ppm byweight to about 1200 ppm by weight. Basic nitrogen can vary from about100 ppm by weight to about 1000 ppm by weight, preferably from about 100ppm by weight to about 600 ppm by weight.

As used herein, the dispersant concentrations are given on an “asdelivered” basis. Typically, the active dispersant is delivered with aprocess oil. The “as delivered” dispersant typically contains from about20 weight percent to about 80 weight percent, or from about 40 weightpercent to about 60 weight percent, of active dispersant in the “asdelivered” dispersant product.

Antioxidants

Antioxidants retard the oxidative degradation of base oils duringservice. Such degradation may result in deposits on metal surfaces, thepresence of sludge, or a viscosity increase in the lubricant. Oneskilled in the art knows a wide variety of oxidation inhibitors that areuseful in lubricating oil compositions. See, Klamann in Lubricants andRelated Products, op cite, and U.S. Pat. Nos. 4,798,684 and 5,084,197,for example.

Useful antioxidants include hindered phenols. These phenolicantioxidants may be ashless (metal-free) phenolic compounds or neutralor basic metal salts of certain phenolic compounds. Typical phenolicantioxidant compounds are the hindered phenolics which are the oneswhich contain a sterically hindered hydroxyl group, and these includethose derivatives of dihydroxy aryl compounds in which the hydroxylgroups are in the o- or p-position to each other. Typical phenolicantioxidants include the hindered phenols substituted with C₆+ alkylgroups and the alkylene coupled derivatives of these hindered phenols.Examples of phenolic materials of this type 2-t-butyl-4-heptyl phenol;2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered mono-phenolic antioxidants may include forexample hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.Bis-phenolic antioxidants may also be advantageously used in combinationwith the instant disclosure. Examples of ortho-coupled phenols include:2,2′-bis(4-heptyl-6-t-butyl-phenol); 2,2′-bis(4-octyl-6-t-butyl-phenol);and 2,2′-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenolsinclude for example 4,4′-bis(2,6-di-t-butyl phenol) and4,4′-methylene-bis(2,6-di-t-butyl phenol).

Effective amounts of one or more catalytic antioxidants may also beused. The catalytic antioxidants comprise an effective amount of a) oneor more oil soluble polymetal organic compounds; and, effective amountsof b) one or more substituted N,N′-diaryl-o-phenylenediamine compoundsor c) one or more hindered phenol compounds; or a combination of both b)and c). Catalytic antioxidants are more fully described in U.S. Pat. No.8,048,833, herein incorporated by reference in its entirety.

Non-phenolic oxidation inhibitors which may be used include aromaticamine antioxidants and these may be used either as such or incombination with phenolics. Typical examples of non-phenolicantioxidants include: alkylated and non-alkylated aromatic amines suchas aromatic monoamines of the formula R⁸R⁹R¹⁰N where R⁸ is an aliphatic,aromatic or substituted aromatic group, R⁹ is an aromatic or asubstituted aromatic group, and R¹⁰ is H, alkyl, aryl or R¹¹S(O)_(X)R¹²where R¹¹ is an alkylene, alkenylene, or aralkylene group, R¹² is ahigher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1or 2. The aliphatic group R⁸ may contain from 1 to about 20 carbonatoms, and preferably contains from about 6 to 12 carbon atoms. Thealiphatic group is a saturated aliphatic group. Preferably, both R⁸ andR⁹ are aromatic or substituted aromatic to groups, and the aromaticgroup may be a fused ring aromatic group such as naphthyl. Aromaticgroups R⁸ and R⁹ may be joined together with other groups such as S.

Typical aromatic amines antioxidants have alkyl substituent groups of atleast about 6 carbon atoms. Examples of aliphatic groups include hexyl,heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups willnot contain more than about 14 carbon atoms. The general types of amineantioxidants useful in the present compositions include diphenylamines,phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenylphenylene diamines. Mixtures of two or more aromatic amines are alsouseful. Polymeric amine antioxidants can also be used. Particularexamples of aromatic amine antioxidants useful in the present disclosureinclude: p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine;phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.

Sulfurized alkyl phenols and alkali or alkaline earth metal saltsthereof also are useful antioxidants.

Preferred antioxidants include hindered phenols, arylamines. Theseantioxidants may be used individually by type or in combination with oneanother. Such additives may be used in an amount of about 0.01 to 5weight percent, preferably about 0.01 to 1.5 weight percent, morepreferably zero to less than 1.5 weight percent, more preferably zero toless than 1 weight percent.

Pour Point Depressants (PPDs)

Conventional pour point depressants (also known as lube oil flowimprovers) may be added to the compositions of the present disclosure ifdesired. These pour point depressant may be added to lubricatingcompositions of the present disclosure to lower the minimum temperatureat which the fluid will flow or can be poured. Examples of suitable pourpoint depressants include polymethacrylates, polyacrylates,polyarylamides, condensation products of haloparaffin waxes and aromaticcompounds, vinyl carboxylate polymers, and terpolymers ofdialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479;2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pourpoint depressants and/or the preparation thereof. Such additives may beused in an amount of about 0.01 to 5 weight percent, preferably about0.01 to 1.5 weight percent.

Seal Compatibility Agents

Seal compatibility agents help to swell elastomeric seals by causing achemical reaction in the fluid or physical change in the elastomer.Suitable seal compatibility agents for lubricating oils include organicphosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzylphthalate, for example), and polybutenyl succinic anhydride. Suchadditives may be used in an amount of about 0.01 to 3 weight percent,preferably about 0.01 to 2 weight percent.

Antifoam Agents

Anti-foam agents may advantageously be added to lubricant compositions.These agents retard the formation of stable foams. Silicones and organicpolymers are typical anti-foam agents. For example, polysiloxanes, suchas silicon oil or polydimethyl siloxane, provide antifoam properties.Anti-foam agents are commercially available and may be used inconventional minor amounts along with other additives such asdemulsifiers; usually the amount of these additives combined is lessthan 1 weight percent and often less than 0.1 weight percent.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protectlubricated metal surfaces against chemical attack by water or othercontaminants. A wide variety of these are commercially available.

One type of antirust additive is a polar compound that wets the metalsurface preferentially, protecting it with a film of oil. Another typeof antirust additive absorbs water by incorporating it in a water-in-oilemulsion so that only the oil touches the metal surface. Yet anothertype of antirust additive chemically adheres to the metal to produce anon-reactive surface. Examples of suitable additives include zincdithiophosphates, metal phenolates, basic metal sulfonates, fatty acidsand amines. Such additives may be used in an amount of about 0.01 to 5weight percent, preferably about 0.01 to 1.5 weight percent.

The types and quantities of performance additives used in combinationwith the instant disclosure in lubricant compositions are not limited bythe examples shown herein as illustrations.

When lubricating oil compositions contain one or more of the additivesdiscussed above, the additive(s) are blended into the composition in anamount sufficient for it to perform its intended function. Typicalamounts of such additives useful in the present disclosure are shown inTable 1 below.

It is noted that many of the additives are shipped from the additivemanufacturer as a concentrate, containing one or more additivestogether, with a certain amount of base oil diluents. Accordingly, theweight amounts in the table below, as well as other amounts mentionedherein, are directed to the amount of active ingredient (that is thenon-diluent portion of the ingredient). The weight percent (wt %)indicated below is based on the total weight of the lubricating oilcomposition.

When lubricating oil compositions contain one or more of the additivesdiscussed above, the additive(s) are blended into the composition in anamount sufficient for it to perform its intended function. Typicalamounts of such additives useful in the present disclosure are shown toin Table 1 below.

It is noted that many of the additives are shipped from the additivemanufacturer as a concentrate, containing one or more additivestogether, with a certain amount of base oil diluents. Accordingly, theweight amounts in the table below, as well as other amounts mentionedherein, are directed to the amount of active ingredient (that is thenon-diluent portion of the ingredient). The weight percent (wt %)indicated below is based on the total weight of the lubricating oilcomposition.

TABLE 1 Typical Amounts of Other Lubricating Oil Components ApproximateApproximate Compound wt % (Useful) wt % (Preferred) Antiwear 0.1-2 0.5-1Dispersant  0.1-20 0.1-8 Detergent  0.1-20 0.1-8 Antioxidant  0.1-100.1-5 Friction Modifier 0.01-10  0.01-1.5 Pour Point Depressant 0.0-5 0.01-1.5 (PPD) Anti-foam Agent 0.001-3   0.001-0.15 Viscosity IndexImprover 0.0-8 0.1-6 (pure polymer basis) Inhibitor and Antirust 0.01-5  0.01-1.5

The foregoing additives are all commercially available materials. Theseadditives may be added independently but are usually precombined inpackages which can be obtained from suppliers of lubricant oiladditives. Additive packages with a variety of ingredients, proportionsand characteristics are available and selection of the appropriatepackage will take the requisite use of the ultimate composition intoaccount.

The following non-limiting examples are provided to illustrate thedisclosure.

EXAMPLES Test Methods

In all Examples herein, unless specified otherwise, the followingproperties are determined pursuant to the following ASTM standards:

Noack Pour Properties KV100 KV40 VI Volatility Point CCSV ASTM StandardD445 D445 D2270 D5800 D5950 D5293

Additional bench testing was conducted for the lubricating oilcompositions or formulations of this disclosure. The additional benchtesting included the following: thermo-oxidation engine oil simulationtesting (TEOST 33C-SAE 932837 and SAE 962039).

Deposit resistance formation of the lubricating oils was compared usinga thermo-oxidation engine oil simulation test (TEOST 33C) measured byASTM D6335. A good result in the TEOST test is defined as less than 80mg, or less than 60 mg, or less than 40 mg, or less than 30 mg, or lessthan 20 mg, or less than 10 mg. TEOST 33C performance results correlatesdirectly with high temperature deposit resistance and engine cleanlinessfor a lubricating oil. Hence, the lower the TEOST 33C total deposits inmilligrams, the cleaner the internal engine components of an internalcombustion engine lubricated with the lubricating oil compositionsdisclosed herein.

Inventive and Comparative Lubricating Oil Compositions

Table 2 below compares physical properties of the various Group I toGroup V base stocks used in the comparative and inventive lubricatingoils of the instant disclosure.

TABLE 2 Base Stock Properties Noack CCS-35C, Pour Point, Aniline Point,KV40 KV100 VI Loss, % cP ° C. ° C. D445 D445 D2270 D5800 D5293 D97 D611Group 1 - 100N 20.4 4.1 99 26.3 5590 −18 98 Group II - 4.5 cSt 22.9 4.6114 13.8 4906 −18 113 Group III - GTL4 18.3 4.1 126 11.9 1757 −37 121Group IV - PAO 4 18.5 4.1 126 11.5 1442 <−60 120 Di-isononyl Phthalate33.4 5.0 55 13.4 −39 <0 ester - Group V

FIG. 1 shows deposit results for partial lubricating oil compositions(no pour point depressant, no antifoam agent, no viscosity modifier orother lubricating oil additives) in order to assess the impact of basestock type, ashless organic friction modifier and overbased detergent oncleanliness performance. The partial lubricating oil compositions ofFIG. 1 include both comparative examples and inventive examples in orderto determine the impact of the ashless organic friction modifier (mixedmono (47%), di (33%) and tri (20%) fatty acids using saturated C₁₆ andC₁₈ alkyl chains) in each of the inventive examples on the hightemperature cleanliness performance as measured by the TEOST 33C deposittest. Each of the inventive lubricating oil compositions of FIG. 1 alsoincluded a high TBN (350 TBN) calcium salicylate detergent at 2 wt. %.Five different base stocks were evaluated in the examples of FIG. 1including a Group I-100 Neutral, a 4.5 cSt Group II, a 4 cSt Group IIIGTL, a 4 cSt Group IV PAO, and a Group V di-isononyl phthalate ester.For all five base stock types, it can be seen that when a combination ofthe ashless organic friction modifier (mixed mono (47%), di (33%) andtri (20%) fatty acids using saturated C₁₆ and C₁₈ alkyl chains) and 350TBN calcium salicylate detergent were used in the partial formulations,the TEOST 33C deposit resistance is significantly lower than if eitherthe ashless organic friction modifier or the overbased detergent or bothwere left out of the lubricating oil compositions. Hence, the surprisingbenefit in deposit resistance when the lubricating oils included asynergistic combination of the ashless organic friction modifier and theoverbased detergent. It can be seen from FIG. 1 that lubricating oilcompositions including a combination of the high TBN calcium salicylatedetergent and the ashless organic friction modifier (mixed mono (47%),di (33%) and tri (20%) fatty acids using saturated C₁₆ and C₁₈ alkylchains) provided for TEOST 33C deposits that were from 32 to 91% lowerthan comparable (comparative) lubricating oil compositions not includingthe ashless organic friction modifier. The improvement in depositresistance for the inventive examples of FIG. 1 relative to thecomparative examples not including the combination of the ashlessorganic friction modifier and the overbased detergent was surprising andunexpected. The improvement in deposit resistance and cleanlinessperformance was also seen across all five groups of base stocks tested.

FIG. 2 shows deposit results for partial lubricating oil compositions(no pour point depressant, no antifoam agent, no viscosity modifier orother lubricating oil additives) in order to assess the impact ofoverbased detergent type in combination with ashless organic frictionmodifier on cleanliness performance. The base stock used for all of thepartial formulations was 4 cSt PAO. The five overbased detergentsevaluated in FIG. 2 included 350 TBN calcium salicylate, 400 TBNmagnesium sulfonate, 400 TBN calcium sulfonate, 255 TBN calcium phenate,and 68 TBN calcium salicylate. For all five overbased detergents, it canbe seen that when a combination of the ashless organic friction modifier(mixed mono (47%), di (33%) and tri (20%) fatty acids using saturatedC16 and C18 alkyl chains) and any of the five overbased detergents wereused in the partial formulations, the TEOST 33C deposit resistance issignificantly lower than if either the ashless organic friction modifieror the overbased detergent or both were left out of the lubricating oilcompositions. Hence, further support for the surprising benefit indeposit resistance when the lubricating oils included a synergisticcombination of the ashless organic friction modifier and the overbaseddetergent across a range of different overbased detergent types. Theimprovement in deposit resistance for the inventive examples of FIG. 2ranged from 17 to 80% lower than comparable comparative examples notincluding the combination of the ashless organic friction modifier andthe overbased detergent. Hence, the improvement in deposit resistanceand cleanliness performance was seen across all five types of overbaseddetergents tested.

FIG. 3 shows deposit results for partial lubricating oil compositions(no pour point depressant, no antifoam agent, no viscosity modifier orother lubricating oil additives) in order to assess the impact ofashless organic friction modifier type in combination with a 350 TBNcalcium salicylate detergent on cleanliness performance. The base stockused for all of the partial formulations was 4 cSt PAO. The ninedifferent ashless organic friction modifiers evaluated in FIG. 3included mixed mono-(47%), di-(33%) and tri-(20%) fatty acids usingsaturated C16 and C18 alkyl chains, glycerol mono-, di- and tri-mixedoleate, propylene glycol stearyl ether, poly-hydroxylcarboxylic acidesters of polyalkylene oxide modified polyols, n-tallow 1,3diaminopropane, oleic acid, oleyl amide, and polymeric organic frictionmodifier containing PIBSA, glycerol and oligomerized ethylene oxide. Thecomposition of the glycerol mono-, di- and tri-mixed oleate utilized wasdetermined by GC-MS analysis with the analysis results indicated in theTable 3 below, which shows that it is mainly glycerol dioleate.

TABLE 3 Glycerol Mixed Oleate Compositional Analysis GLYCEROL MIXEDOLEATE Wt. % (value in parentheses Area % based on GC-MS based on GPCtrace) Ocatdecadienoic acid  6.3 Glycerol monooleate 13.3 (16.2)Glycerol dioleate 42.3 (42.6) Triglycerides 14.5 Other 23.6 (41.2 -including triglycerides)

For all nine ashless organic friction modifiers evaluated, it can beseen that when a combination of any of one of the nine ashless organicfriction modifiers was used in combination with a 350 TBN calciumsalicylate detergent in the partial formulations, the TEOST 33C depositresistance is significantly lower than if either the ashless organicfriction modifier or the overbased detergent or both were left out ofthe lubricating oil compositions. Hence, further support for thesurprising benefit in deposit resistance when the lubricating oilsincluded a synergistic combination of the ashless organic frictionmodifier and the overbased detergent across a range of different ashlessorganic friction modifier types. The improvement in deposit resistancefor the inventive examples of FIG. 3 ranged from 14 to 88% lower thancomparable comparative examples not including the combination of theashless organic friction modifier and the overbased detergent. Hence,the improvement in deposit resistance and cleanliness performance wasseen across all nine types of ashless organic friction modifiers tested.

FIG. 4 (tabular form) and FIG. 5 (graphical form) show deposit resultsfor partial lubricating oil compositions (no pour point depressant, noantifoam agent, no viscosity modifier or other lubricating oiladditives) in order to assess the impact of ashless organic frictionmodifier loading level or concentration on cleanliness performance. Theashless organic friction modifier evaluated was a mixed mono-(47%),di-(33%) and tri-(20%) fatty acids using saturated C16 and C18 alkylchains across a loading range in the partial formulation of 0 to 1 wt.%. The detergent used was 350 TBN calcium salicylate detergent at 2 wt.%. The base stock used for all of the partial formulations was 4 cStPAO. It can be seen from FIGS. 4 and 5 that the TEOST 33C depositsdecrease as the loading level of the mixed mono-(47%), di-(33%) andtri-(20%) fatty acids using saturated C16 and C18 alkyl chains ashlessorganic friction modifier increases in the inventive formulations.Relative to the comparative examples in FIG. 4, which do not includeboth the ashless organic friction modifier and the overbased detergent,the inventive examples provided a 21% to 91% decrease in TEOST 33Cdeposits, which is surprising and unexpected.

In summary, it has been discovered that by employing a combination of anashless organic friction modifier and an overbased detergent inlubricating oil formulations, high deposit resistance is improvedsignificantly in comparison to comparable lubricating oils not includinga combination of the ashless organic friction modifier and the overbaseddetergent.

PCT and EP Clauses:

1. A lubricating oil composition comprising:

a lubricating oil base stock at from 20 to 95 wt % of the composition,at least one ashless organic friction modifier at from 0.1 to 20 wt % ofthe composition, at least one overbased detergent at from 0.1 to 20 wt %of the composition, and wherein the remainder of the lubricating oilcomposition includes one or more other lubricating oil additives;

wherein the at least one ashless organic friction modifier is selectedfrom the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane; a polymeric organic friction modifiercontaining PIBSA, glycerol and oligomerized ethylene oxide andcombinations thereof; and

wherein the deposit resistance as measured by TEOST 33C total deposits(ASTM D6335) is at least 20% lower than the deposit resistance for acomparable lubricating oil composition not including the combination ofthe at least one ashless organic friction modifier and the at least oneoverbased detergent.

2. The composition of clause 1, wherein the lubricating oil base stockis selected from the from the group consisting of a Group I base stock,a Group II base stock, a Group III base stock, a Group IV base stock, aGroup V base stock and combinations thereof.

3. The composition of clauses 1-2, wherein the lubricating oil basestock is from 85 to 95 wt % of the lubricating oil composition.

4. The composition of clauses 1-3, wherein the lubricating oil basestock is selected from the group consisting of a 100N Group I basestock, a 4.5 cSt Group II base stock, a 4 cSt gas to liquids (GTL) basestock, a 4 cSt polyalphaolefin (PAO) base stock, a di-isononyl phthalateester base stock and combinations thereof.

5. The composition of clauses 1-4, wherein the at least one overbaseddetergent is metal containing detergent including sulfonates, phenates,salicylates, carboxylates and combinations thereof and having a TotalBase Number (TBN) ranging between 60 and 600.

6. The composition of clause 5, wherein the at least one overbaseddetergent is selected from the group consisting of 350 TBN calciumsalicylate, 400 TBN magnesium sulfonate, 400 TBN calcium sulfonate, 255TBN calcium phenate, 68 TBN calcium salicylate and combinations thereof.

7. The composition of clauses 1-6, wherein the at least one ashlessorganic friction modifier is selected from the group consisting of mixedmono-(47%), di-(33%) and tri-(20%) fatty acids using saturated C16 andC18 alkyl chains, glycerol mono-, di- and tri-mixed oleate, propyleneglycol stearyl ether, poly-hydroxylcarboxylic acid esters ofpolyalkylene oxide modified polyols, oleic acid, oleyl amide, andcombinations thereof.

8. The composition of clause 7, wherein the at least one ashless organicfriction modifier is mixed mono-(47%), di-(33%) and tri-(20%) fattyacids using saturated C16 and C18 alkyl chains at from 0.1 to 2.0 wt %of the lubricating oil composition.

9. The composition of clauses 1-8, wherein the deposit resistance asmeasured by TEOST 33C total deposits (ASTM D6335) is less than or equalto 75 mg.

10. The composition of clauses 1-9, wherein the one or more otherlubricating oil additives are selected from the group consisting of ananti-wear additive, viscosity index improver, antioxidant, dispersant,pour point depressant, corrosion inhibitor, metal deactivator, sealcompatibility additive, anti-foam agent, inhibitor, anti-rust additive,and ash forming metal containing friction modifier.

11. The composition of clause 10, wherein the one or more otherlubricating oil additives range from 1 to 10 wt % of the lubricating oilcomposition and include a combination of a PIBSA/PAM dispersant, a C3/C6secondary ZDDP antiwear additive, and a diphenylamine antioxidant.

12. The composition of clauses 1-11, wherein the lubricating oil basestock has a kinematic viscosity at 100 deg. C. ranging from 2.5 to 12cSt.

13. The composition of clauses 1-12, wherein lubricating oil compositionis an SAE viscosity grade selected from the group consisting of 0W-30,5W-30, 0W-20, 5W-20, 0W-16, 5W-16, 0W-12, 5W-12, 0W-8, and 5W-8.

14. The composition of clauses 1-13, wherein the lubricating oilcomposition is a passenger vehicle engine oil (PVEO) or a commercialvehicle engine oil (CVEO).

15. A method for improving the high temperature deposit resistance of alubricating oil composition for use in lubricating a mechanicalcomponent comprising:

providing a lubricating oil composition to a mechanical component,wherein the lubricating oil composition comprises: a lubricating oilbase stock at from 20 to 95 wt % of the composition, at least oneashless organic friction modifier at from 0.1 to 20 wt % of thecomposition, at least one overbased detergent at from 0.1 to 20 wt % ofthe composition, and wherein the remainder of the lubricating oilcomposition includes one or more other lubricating oil additives;

wherein the at least one ashless organic friction modifier is selectedfrom the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino;

n-tallow 1,3 diaminopropane;

a polymeric organic friction modifier containing PIBSA, glycerol andoligomerized ethylene oxide and combinations thereof; and

-   -   wherein the deposit resistance as measured by TEOST 33C total        deposits (ASTM D6335) is at least 20% lower than the deposit        resistance for a comparable lubricating oil composition not        including the combination of the at least one ashless organic        friction modifier and the at least one overbased detergent.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this disclosure and for all jurisdictions in whichsuch incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

The present disclosure has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1. A lubricating oil composition comprising: a lubricating oil basestock at from 20 to 95 wt % of the composition, at least one ashlessorganic friction modifier at from 0.1 to 20 wt % of the composition, atleast one overbased detergent at from 0.1 to 20 wt % of the composition,and wherein the remainder of the lubricating oil composition includesone or more other lubricating oil additives; wherein the at least oneashless organic friction modifier is selected from the group consistingof

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino; n-tallow 1,3 diaminopropane; apolymeric organic friction modifier containing PIBSA, glycerol andoligomerized ethylene oxide and combinations thereof; and wherein thedeposit resistance as measured by TEOST 33C total deposits (ASTM D6335)is at least 20% lower than the deposit resistance for a comparablelubricating oil composition not including the combination of the atleast one ashless organic friction modifier and the at least oneoverbased detergent.
 2. The composition of claim 1, wherein thelubricating oil base stock is selected from the from the groupconsisting of a Group I base stock, a Group II base stock, a Group IIIbase stock, a Group IV base stock, a Group V base stock and combinationsthereof.
 3. The composition of claim 1, wherein the lubricating oil basestock is from 85 to 95 wt % of the lubricating oil composition.
 4. Thecomposition of claim 3, wherein the lubricating oil base stock isselected from the group consisting of a 100N Group I base stock, a 4.5cSt Group II base stock, a 4 cSt gas to liquids (GTL) base stock, a 4cSt polyalphaolefin (PAO) base stock, a di-isononyl phthalate ester basestock and combinations thereof.
 5. The composition of claim 1, whereinthe at least one overbased detergent is metal containing detergentincluding sulfonates, phenates, salicylates, carboxylates andcombinations thereof and having a Total Base Number (TBN) rangingbetween 60 and
 600. 6. The composition of claim 5, wherein the at leastone overbased detergent is selected from the group consisting of 350 TBNcalcium salicylate, 400 TBN magnesium sulfonate, 400 TBN calciumsulfonate, 255 TBN calcium phenate, 68 TBN calcium salicylate andcombinations thereof.
 7. The composition of claim 1, wherein the atleast one ashless organic friction modifier is selected from the groupconsisting of mixed mono-(47%), di-(33%) and tri-(20%) fatty acids usingsaturated C16 and C18 alkyl chains, glycerol mono-, di- and tri-mixedoleate, propylene glycol stearyl ether, poly-hydroxylcarboxylic acidesters of polyalkylene oxide modified polyols, oleic acid, oleyl amide,and combinations thereof.
 8. The composition of claim 7, wherein the atleast one ashless organic friction modifier is mixed mono-(47%),di-(33%) and tri-(20%) fatty acids using saturated C16 and C18 alkylchains at from 0.1 to 2.0 wt % of the lubricating oil composition. 9.The composition of claim 1, wherein the deposit resistance as measuredby TEOST 33C total deposits (ASTM D6335) is less than or equal to 75 mg.10. The composition of claim 1, wherein the one or more otherlubricating oil additives are selected from the group consisting of ananti-wear additive, viscosity index improver, antioxidant, dispersant,pour point depressant, corrosion inhibitor, metal deactivator, sealcompatibility additive, anti-foam agent, inhibitor, anti-rust additive,and ash forming metal containing friction modifier.
 11. The compositionof claim 1, wherein the one or more other lubricating oil additivesrange from 1 to 10 wt % of the lubricating oil composition and include acombination of a PIBSA/PAM dispersant, a C3/C6 secondary ZDDP antiwearadditive, and a diphenylamine antioxidant.
 12. The composition of claim1, wherein the lubricating oil base stock has a kinematic viscosity at100 deg. C. ranging from 2.5 to 12 cSt.
 13. The composition of claim 1,wherein lubricating oil composition is an SAE viscosity grade selectedfrom the group consisting of 0W-30, 5W-30, 0W-20, 5W-20, 0W-16, 5W-16,0W-12, 5W-12, 0W-8, and 5W-8.
 14. The composition of claim 1, whereinthe lubricating oil composition is a passenger vehicle engine oil (PVEO)or a commercial vehicle engine oil (CVEO).
 15. A method for improvingthe high temperature deposit resistance of a lubricating oil compositionfor use in lubricating a mechanical component comprising: providing alubricating oil composition to a mechanical component, wherein thelubricating oil composition comprises: a lubricating oil base stock atfrom 20 to 95 wt % of the composition, at least one ashless organicfriction modifier at from 0.1 to 20 wt % of the composition, at leastone overbased detergent at from 0.1 to 20 wt % of the composition, andwherein the remainder of the lubricating oil composition includes one ormore other lubricating oil additives; wherein the at least one ashlessorganic friction modifier is selected from the group consisting of

wherein A and B are each independently H, a C1-C24 alkyl, or a C2-C24alkenyl;

wherein A, B and C are each independently H, a C1-C24 alkyl, a C2-C24alkenyl, a C1-C24 alkylcarbonyl, and a C1-C24 alkenylcarbonyl;

wherein A is a C1-C24 alkyl, or a C2-C24 alkenyl and B is O, an amino, aC1-C8 alkylamino or a C1-C8 dialkylamino; n-tallow 1,3 diaminopropane; apolymeric organic friction modifier containing PIBSA, glycerol andoligomerized ethylene oxide and combinations thereof; and wherein thedeposit resistance as measured by TEOST 33C total deposits (ASTM D6335)is at least 20% lower than the deposit resistance for a comparablelubricating oil composition not including the combination of the atleast one ashless organic friction modifier and the at least oneoverbased detergent.
 16. The method of claim 15, wherein the lubricatingoil base stock is selected from the from the group consisting of a GroupI base stock, a Group II base stock, a Group III base stock, a Group IVbase stock, a Group V base stock and combinations thereof.
 17. Themethod of claim 15, wherein the lubricating oil base stock is from 85 to95 wt % of the lubricating oil composition.
 18. The method of claim 15,wherein the lubricating oil base stock is selected from the groupconsisting of a 100N Group I base stock, a 4.5 cSt Group II base stock,a 4 cSt gas to liquids (GTL) base stock, a 4 cSt polyalphaolefin (PAO)base stock, a di-isononyl phthalate ester base stock and combinationsthereof.
 19. The method of claim 15, wherein the at least one overbaseddetergent is metal containing detergent including sulfonates, phenates,salicylates, carboxylates and combinations thereof and having a TotalBase Number (TBN) ranging between 60 and
 600. 20. The method of claim19, wherein the at least one overbased detergent is selected from thegroup consisting of 350 TBN calcium salicylate, 400 TBN magnesiumsulfonate, 400 TBN calcium sulfonate, 255 TBN calcium phenate, 68 TBNcalcium salicylate and combinations thereof.
 21. The method of claim 15,wherein the at least one ashless organic friction modifier is selectedfrom the group consisting of mixed mono-(47%), di-(33%) and tri-(20%)fatty acids using saturated C16 and C18 alkyl chains, glycerol mono-,di- and tri-mixed oleate, propylene glycol stearyl ether,poly-hydroxylcarboxylic acid esters of polyalkylene oxide modifiedpolyols, oleic acid, oleyl amide, and combinations thereof.
 22. Themethod of claim 21, wherein the at least one ashless organic frictionmodifier is mixed mono-(47%), di-(33%) and tri-(20%) fatty acids usingsaturated C16 and C18 alkyl chains at from 0.1 to 2.0 wt % of thelubricating oil composition.
 23. The method of claim 15, wherein thedeposit resistance as measured by TEOST 33C total deposits (ASTM D6335)is less than or equal to 75 mg.
 24. The method of claim 15, wherein theone or more other lubricating oil additives are selected from the groupconsisting of an anti-wear additive, viscosity index improver,antioxidant, dispersant, pour point depressant, corrosion inhibitor,metal deactivator, seal compatibility additive, anti-foam agent,inhibitor, anti-rust additive, and ash forming metal containing frictionmodifier.
 25. The method of claim 24, wherein the one or more otherlubricating oil additives range from 1 to 10 wt % of the lubricating oilcomposition and include a combination of a PIBSA/PAM dispersant, a C3/C6secondary ZDDP antiwear additive, and a diphenylamine antioxidant. 26.The method of claim 15, wherein the lubricating oil base stock has akinematic viscosity at 100 deg. C. ranging from 2.5 to 12 cSt.
 27. Themethod of claim 15, wherein the mechanical component is selected fromthe group consisting of internal combustion engines, power trains,drivelines, transmissions, gears, gear trains, gear sets, compressors,pumps, hydraulic systems, bearings, bushings, turbines, pistons, pistonrings, cylinder liners, cylinders, cams, tappets, lifters, bearings(journal, roller, tapered, needle, ball), gears and valves.
 28. Themethod of claim 27, wherein the mechanical component is an internalcombustion engine.
 29. The method of claim 28, wherein lubricating oilcomposition is an SAE viscosity grade selected from the group consistingof 0W-30, 5W-30, 0W-20, 5W-20, 0W-16, 5W-16, 0W-12, 5W-12, 0W-8, and5W-8.
 30. The method of claim 29, wherein the lubricating oilcomposition is a passenger vehicle engine oil (PVEO) or a commercialvehicle engine oil (CVEO).